WO2015151833A1 - Composition photodurcissable et encre photodurcissable pour jet d'encre la contenant, procédé d'enregistrement utilisant la composition photodurcissable, et procédé d'enregistrement utilisant l'encre photodurcissable pour jet d'encre - Google Patents

Composition photodurcissable et encre photodurcissable pour jet d'encre la contenant, procédé d'enregistrement utilisant la composition photodurcissable, et procédé d'enregistrement utilisant l'encre photodurcissable pour jet d'encre Download PDF

Info

Publication number
WO2015151833A1
WO2015151833A1 PCT/JP2015/058252 JP2015058252W WO2015151833A1 WO 2015151833 A1 WO2015151833 A1 WO 2015151833A1 JP 2015058252 W JP2015058252 W JP 2015058252W WO 2015151833 A1 WO2015151833 A1 WO 2015151833A1
Authority
WO
WIPO (PCT)
Prior art keywords
photocurable
photocurable composition
inkjet ink
ink
mass
Prior art date
Application number
PCT/JP2015/058252
Other languages
English (en)
Japanese (ja)
Inventor
雅士 宮野
孝由 戸枝
Original Assignee
コニカミノルタ株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=54240164&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=WO2015151833(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by コニカミノルタ株式会社 filed Critical コニカミノルタ株式会社
Priority to JP2016511530A priority Critical patent/JP6536570B2/ja
Priority to US15/127,636 priority patent/US10011665B1/en
Publication of WO2015151833A1 publication Critical patent/WO2015151833A1/fr

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/0041—Digital printing on surfaces other than ordinary paper
    • B41M5/0064—Digital printing on surfaces other than ordinary paper on plastics, horn, rubber, or other organic polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/32—Inkjet printing inks characterised by colouring agents
    • C09D11/322—Pigment inks
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/38—Inkjet printing inks characterised by non-macromolecular additives other than solvents, pigments or dyes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
    • B41J11/00—Devices or arrangements  of selective printing mechanisms, e.g. ink-jet printers or thermal printers, for supporting or handling copy material in sheet or web form
    • B41J11/0015—Devices or arrangements  of selective printing mechanisms, e.g. ink-jet printers or thermal printers, for supporting or handling copy material in sheet or web form for treating before, during or after printing or for uniform coating or laminating the copy material before or after printing
    • B41J11/002—Curing or drying the ink on the copy materials, e.g. by heating or irradiating
    • B41J11/0021—Curing or drying the ink on the copy materials, e.g. by heating or irradiating using irradiation
    • B41J11/00214—Curing or drying the ink on the copy materials, e.g. by heating or irradiating using irradiation using UV radiation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/0041—Digital printing on surfaces other than ordinary paper
    • B41M5/0047—Digital printing on surfaces other than ordinary paper by ink-jet printing
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F216/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
    • C08F216/12—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
    • C08F216/125—Monomers containing two or more unsaturated aliphatic radicals, e.g. trimethylolpropane triallyl ether or pentaerythritol triallyl ether
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/102—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/103—Esters of polyhydric alcohols or polyhydric phenols of trialcohols, e.g. trimethylolpropane tri(meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/104—Esters of polyhydric alcohols or polyhydric phenols of tetraalcohols, e.g. pentaerythritol tetra(meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/12—Polypropene

Definitions

  • the present invention relates to a photocurable composition and a photocurable inkjet ink containing the photocurable composition, and further relates to a recording method using the photocurable composition and a photocurable composition containing the photocurable composition.
  • the present invention relates to a recording method using an ink jet ink.
  • the ink jet recording method is used in various printing fields because it can form an image easily and inexpensively.
  • As one of the ink jet recording methods there is an ultraviolet curable ink jet method in which droplets of ultraviolet curable ink are landed on a recording medium and then cured by irradiation with ultraviolet rays to form an image.
  • the ultraviolet curable ink jet method has been attracting attention in recent years because it can form an image having high scratch resistance and adhesion even on a recording medium having no ink absorbability.
  • Patent Document 1 Japanese Patent Laid-Open No. 2011-225751 which discloses that the adhesion is improved by containing a polyester resin in the ultraviolet curable ink, or styrene or a styrene derivative as a polymer or a copolymer.
  • JP-A-2013-249357 discloses that adhesion can be improved by adding a polymer component containing at least one acrylic ester or acrylic acid.
  • Patent Document 3 Japanese Patent Laid-Open No. 2012-1626466 discloses that the adhesion is improved by adding a polyfunctional acrylate as a polyfunctional photopolymerizable monomer and adding silica fine particles or an oligomer (varnish). ) Is also known.
  • Curing shrinkage which is a problem, is a phenomenon caused by photopolymerizable compounds existing at van der Waals distance being polymerized and covalently bonded to each other by UV irradiation before curing. That is, it is considered that volume shrinkage occurs because the covalent bond distance is shorter than the van der Waals distance, which leads to deformation of the non-absorbent medium.
  • the inventor of the present application adds a metal chelate compound to the photopolymerizable composition and substitutes for a coordination bond having a longer bond distance than a covalent bond, thereby suppressing curing shrinkage while maintaining adhesion. Found that you can.
  • An object of the present invention is to provide a photocurable composition and a photocurable inkjet ink that can suppress curing shrinkage while maintaining adhesion.
  • the invention described in item (1) contains a photopolymerizable compound and a photoinitiator
  • the photopolymerizable compound is a radical polymerizable monomer
  • the photoinitiator is a photocurable composition that is a photoradical initiator
  • the photocurable composition contains a metal chelate compound
  • the central metal element of the metal chelate compound is selected from any of Groups 2, 4, 8, and 13, and the metal chelate compound is 0.1% by mass with respect to the total mass of the photocurable composition. It is contained at 5% by mass or less.
  • the invention described in item (2) is the photocurable composition described in item (1),
  • the metal chelate compound is contained in a state dissolved in the photocurable composition.
  • the invention described in item (3) is the photocurable composition described in item (1) or item (2),
  • the photocurable composition contains a crosslinking accelerator, the crosslinking accelerator has an active methylene moiety as a partial structure, and the content of the crosslinking accelerator is 5 with respect to the mass of the entire photocurable composition. It is characterized by being not less than 30% by mass and not more than 30% by mass.
  • the invention described in item (4) is the photocurable composition according to any one of items (1) to (3),
  • the photocurable composition contains an organic solvent, and the content of the organic solvent is 3% by mass or less based on the total mass of the photocurable composition.
  • the invention described in item (5) is a photocurable inkjet ink,
  • the photocurable composition according to any one of items (1) to (4) is contained.
  • the invention described in item (6) is the photocurable inkjet ink described in item (5),
  • the photo-curable ink-jet ink contains a color material.
  • the invention described in item (7) is the photocurable inkjet ink described in item (6),
  • the color material is a pigment, and further contains a pigment dispersant.
  • the invention described in item (8) is a recording method using a photocurable composition.
  • the photocurable composition according to any one of items (1) to (4) is applied to a recording medium, and then the photocurable composition is cured by irradiating with actinic rays.
  • the invention described in item (9) is the recording method using the photocurable composition described in item (8).
  • the recording medium is one of polypropylene, polyethylene, and polyethylene terephthalate.
  • the invention described in item (10) is a recording method using a photocurable inkjet ink.
  • An inkjet head for discharging the photocurable inkjet ink according to any one of Items (5) to (7);
  • An irradiation unit for irradiating actinic rays;
  • a recording method using a photocurable inkjet ink in an inkjet recording apparatus comprising a conveyance unit that conveys a recording medium, After the photocurable inkjet ink is applied to the recording medium by the inkjet head, the photocurable inkjet ink is cured by irradiation with actinic rays by the irradiation unit.
  • the invention described in item (11) is the recording method using the photocurable inkjet ink described in item (10).
  • the recording medium is one of polypropylene, polyethylene, and polyethylene terephthalate.
  • a photocurable composition and a photocurable inkjet ink that can suppress curing shrinkage while maintaining adhesion.
  • the photocurable composition according to the present invention is capable of forming an image even on a non-absorbing recording medium by applying a primer layer before forming an image on a substrate by inkjet or the like. Moreover, it can also be set as the photocurable inkjet ink which can form a high-definition image with respect to a medium by containing color materials, such as a pigment, in the photocurable composition mentioned above. Below, the photocurable composition mentioned above is explained in full detail.
  • the photopolymerizable compound in the present invention is a compound that undergoes photopolymerization and becomes a cured product when irradiated with ultraviolet rays, and any known photopolymerizable monomer and / or photopolymerizable oligomer can be used.
  • the term “and / or” in the present invention means that it may be a photopolymerizable monomer or an oligomer, and may further include both. In the following description, the monomer or oligomer is referred to as a photopolymerizable compound.
  • a radical polymerizable monomer can be used in the present invention, and for example, a compound having a (meth) acrylate group, a vinyl group, an allyl ether group, and a maleimide group is used.
  • a compound having a (meth) acrylate group is used as the radical polymerizable monomer.
  • (meth) acrylate compounds and vinyl ether compounds are preferably used from the viewpoint of curability.
  • examples of the radical polymerizable monomer include a vinyl ether compound.
  • examples of monofunctional vinyl ether compounds include methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, n-butyl vinyl ether, t-butyl vinyl ether, 2-ethylhexyl vinyl ether, n-nonyl vinyl ether, lauryl vinyl ether, cyclohexyl vinyl ether, Cyclohexylmethyl vinyl ether, 4-methylcyclohexylmethyl vinyl ether, benzyl vinyl ether, dicyclopentenyl vinyl ether, 2-dicyclopentenoxyethyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, butoxyethyl vinyl ether, methoxyethoxyethyl vinyl ether, ethoxyethoxyethyl vinyl ether , Metoki Polyethylene glycol vinyl ether, te
  • polyfunctional vinyl ether compound examples include, for example, ethylene glycol divinyl ether, diethylene glycol divinyl ether (DEGDVE), polyethylene glycol divinyl ether, propylene glycol divinyl ether, butylene glycol divinyl ether, hexanediol divinyl ether, bisphenol A alkylene oxide di Divinyl ethers such as vinyl ether and bisphenol F alkylene oxide divinyl ether; trimethylol ethane trivinyl ether, trimethylolpropane trivinyl ether, ditrimethylolpropane tetravinyl ether, glycerin trivinyl ether, pentaerythritol tetravinyl ether, dipentaerythritol pentavinyl ether , Dipentaerythritol hexavinyl ether, ethylene oxide-added trimethylolpropane trivinyl ether,
  • Examples of compounds that can be preferably used in the present invention include ethylene oxide (EO) -modified monomers having 6 or more ethylene oxide groups. Since such an EO-modified monomer has an oxygen atom in the ethylene oxide group, there are many sites that can be relatively loosely coordinated with the metal chelate compound. Therefore, the effect of the present invention can be exhibited more effectively.
  • EO ethylene oxide
  • polymerizable oligomers can be blended in the same manner as the monomer.
  • examples of the polymerizable oligomer include epoxy acrylate, aliphatic urethane acrylate, aromatic urethane acrylate, polyester acrylate, and linear acrylic oligomer.
  • the content of the photopolymerizable compound can be appropriately set by other additives such as a metal chelate described later, but is 60% by mass to 95% by mass with respect to the total mass of the photocurable composition. It is preferable to contain.
  • the photoinitiator (photoinitiator) according to the present invention is capable of initiating polymerization of a polymerizable compound by light, and as a photoinitiator, “Application and Market of UV / EB Curing Technology” (CMC) Any known photoinitiator published in the publication, edited by Yoneho Tabata / edited by Radtech Research Association) can be used.
  • a radical polymerization initiator is preferably used, but a cationic polymerization initiator may be further contained.
  • the radical polymerization initiator contained in the photocurable composition of the present invention may be either a molecular cleavage type or a hydrogen abstraction type.
  • Preferred examples of the radical polymerization initiator include benzoin isobutyl ether, 2,4-diethylthioxanthone, 2-isopropylthioxanthone, benzyl, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2-benzyl-2-dimethylamino- 1- (4-morpholinophenyl) -butan-1-one, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine Oxides and the like are included.
  • examples of molecular cleavage type radical polymerization initiators other than these include 1-hydroxycyclohexyl phenyl ketone, benzoin ethyl ether, benzyldimethyl ketal, 2-hydroxy-2-methyl-1-phenylpropan-1-one, -(4-Isopropylphenyl) -2-hydroxy-2-methylpropan-1-one and 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 1- [4- (2 -Hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one and the like.
  • examples of the hydrogen abstraction type photoinitiator include benzophenone, 4-phenylbenzophenone, isophthalphenone, 4-benzoyl-4′-methyl-diphenyl sulfide, and bis (2,4-cyclohexane) which is a metallocene type polymerization initiator.
  • a sensitizer may be contained together with the radical polymerization initiator.
  • sensitizers include trimethylamine, methyldimethanolamine, triethanolamine, p-diethylaminoacetophenone, ethyl p-dimethylaminobenzoate, isoamyl p-dimethylaminobenzoate, N, N-dimethylbenzylamine and 4, Examples include amines that do not cause an addition reaction with a photopolymerizable compound, such as 4′-bis (diethylamino) benzophenone.
  • the radical polymerization initiator and the sensitizer are preferably excellent in solubility in the photopolymerizable compound.
  • the contents of the radical polymerization initiator and the sensitizer are each 0.1 to 20% by mass, preferably 1 to 12% by mass, based on the total mass of the photocurable composition.
  • a dendrimer core described in European Patent 1,674,499A is bound to an amine-based initiator as an initiator structure, European Patent 2,161,264A, European Patent No.
  • An initiator having a polymerizable group described in the specification of 2,189,477A, an amine-based initiator, and a plurality of amine-based initiators described in EP 1,927,632B1 are contained in one molecule.
  • the maleimide-containing polymerizable monomer itself can function as an initiator.
  • the photocurable composition of the present invention may further contain a cationic polymerization initiator (see Organic Electronics Materials Research Group, “Organic Materials for Imaging”, Bunshin Publishing (1993), pages 187 to 192).
  • a cationic polymerization initiator see Organic Electronics Materials Research Group, “Organic Materials for Imaging”, Bunshin Publishing (1993), pages 187 to 192.
  • compounds suitable for the present invention include (C 6 F 5 ) 4 ⁇ , PF 6 ⁇ , AsF 6 ⁇ , SbF 6 ⁇ , CF of aromatic onium compounds such as diazonium, ammonium, iodonium, sulfonium and phosphonium. 3 SO 3 - salts, sulfonated materials that generate a sulfonic acid, halide that photogenerate a hydrogen halide, and can be exemplified iron arene complex.
  • the photocurable composition contains a metal chelate compound.
  • the metal chelate compound in the present invention has a configuration in which a plurality of ligands such as molecules and ions are coordinated to a metal element.
  • the plurality of ligands may be the same or different.
  • the metal element constituting the metal chelate compound of the present invention is Group 2, Group 4, Group 8, or Group 13.
  • a metal element such as Be, Mg, and Ca
  • a metal element such as Ti, Zr, and Hf
  • a group 8 metal element such as Ti, Zr, and Hf
  • a metal element such as Os or a group 13 metal element
  • a metal element such as B, Al, or Ga
  • a ligand of the metal chelate compound of the present invention for example, as a bidentate ligand, ethylenediamine (en), bipyridine (bpy), phenanthroline (phen), BINAP, catecholate, 2,4-pentanedionate, 2 , 4-hexane dionate, 3,5-heptane dionate and the like.
  • the tridentate or higher polydentate ligand include terpyridine (tpy), ethylenediaminetetraacetic acid (edta), porphyrin, cyclam, and crown ethers.
  • metal chelate compounds having a ligand of 2,4-pentanedionate or 2,4-hexanedionate.
  • the ligand which comprises a metal chelate compound may be comprised from the same ligand.
  • the metal chelate compound contained in a photocurable composition is not limited to single, You may mix and contain multiple types.
  • a photo-curable composition containing only a photo-polymerizable compound is markedly cured by shrinkage because the photo-polymerizable compounds are covalently bonded to each other when irradiated with ultraviolet rays to form a cured product.
  • the photopolymerizable compound existing at the van der Waals distance is replaced with a covalent bond distance shorter than the van der Waals distance by irradiation with ultraviolet rays. Therefore, in the present invention, by including a metal chelate compound in the photocurable composition, it is possible to substitute a coordination bond having a bond length longer than that of a covalent bond, so that curing shrinkage is maintained while maintaining adhesion. I guess it was possible to suppress this.
  • the reason why the bond can be replaced with a coordinate bond having a bond length longer than that of a covalent bond is estimated as follows.
  • the photocurable composition is irradiated with ultraviolet rays, the radically polymerizable monomers are covalently bonded to each other to form a cured product.
  • a metal chelate compound is contained therein, the radical polymerization contained in the cured product is performed. It is estimated that a polar bond such as a carbonyl group, an ester group, or an ether group derived from a functional monomer can be coordinated with a metal chelate compound to incorporate a coordinate bond in the cured product.
  • the content of the metal chelate compound is 0.1% by mass or more and 5% by mass or less with respect to the total mass of the photocurable composition from the viewpoint of obtaining an effect of improving adhesion while suppressing curing shrinkage. preferable. Moreover, it is preferable that the metal chelate compound is dissolved as a complex in the photocurable composition from the viewpoint of coordination with the photopolymerizable monomer and suppressing curing shrinkage.
  • Crosslinking accelerator It is more preferable to further include a crosslinking accelerator in the photocurable composition of the present invention, and adhesion can be improved while suppressing curing shrinkage.
  • the crosslinking accelerator can be used regardless of a cyclic structure or a chain structure as long as it is a compound having an active methylene portion that is methylene surrounded by an electronegative group.
  • Examples of the crosslinking accelerator include diketone compounds, ketoester compounds, diester compounds, ketoamide compounds, and cyanoacetic acid compounds.
  • the hydrogen in the active methylene part of the crosslinking accelerator is easily extracted and can be a radical polymerization starting point.
  • the cross-linking accelerator having an active methylene part is easily taken into the cured product as compared with the cross-linking accelerator having no active methylene part, and thus the adhesion can be improved. Furthermore, a structure having a radical polymerizable group in the molecule of the crosslinking accelerator is more preferable in view of further improving adhesion because it is easily taken in by the cured product of the photocurable composition.
  • the mechanism by which the adhesion is further improved by adding the above-described crosslinking accelerator is presumed as follows. It is considered that the coordination bond with the metal chelate compound can be promoted by the addition of a crosslinking accelerator having an active methylene moiety.
  • the active methylene part of the crosslinking accelerator has two electronegative polar groups in close proximity via the methylene group, so that it acts as a bidentate ligand for the metal chelate compound and coordinates effectively. It is thought to combine.
  • the crosslinking accelerator incorporated into the cured product can effectively coordinate bond with the metal chelate, it suppresses curing shrinkage by coordination bonding and also increases the crosslinking density by promoting crosslinking, so that curing shrinkage is suppressed. It is estimated that the adhesion could be further improved while suppressing.
  • the number of ligands of the metal chelate compound is preferably bidentate from the viewpoint of improving adhesion while coordinating the crosslinking accelerator and the metal chelate compound to further suppress curing shrinkage. Moreover, it is preferable to contain in 5 to 30 mass% with respect to the mass of the whole photocurable composition.
  • the photocurable composition of the present invention preferably further contains a radical polymerization inhibitor from the viewpoint of storage stability.
  • radical polymerization inhibitors include phenolic hydroxyl group-containing compounds, quinones or hydroquinones, phenothiazines, N-oxyls, aromatic amines or phenylenediamines, imines, sulfonamides, oximes, hydroxylamines, urea derivatives (eg urea Or thiourea), phosphorus-containing compounds (eg triphenylphosphine, triphenylphosphite, hypophosphorous acid, trinonyl phosphite, triethylphosphite or diphenylisopropylphosphine), sulfur-containing compounds (eg diphenyl sulfide, phenothiazine), And sulfur-containing natural substances (for example, cysteine).
  • phenolic hydroxyl group-containing compounds eg quinones or hydroquinones, phenothiazines, N-oxyls, aromatic amines or phenylenediamines, im
  • TAA tetraazaannulene
  • metal salts such as carbonic acid, chloride, dithiocarbamic acid, sulfuric acid, salicylic acid, acetic acid, stearic acid, and ethylhexanoic acid (copper, manganese, cerium, nickel, chromium, etc.).
  • the content of the radical polymerization inhibitor in the photocurable composition of the present invention is preferably 0.01 or more and 2.0% by mass or less with respect to the total mass of the photocurable composition, and is 0.1 or more and 1 More preferably, it is 8 mass% or less. If it is 0.01% by mass or more, desired photocurable composition storage stability can be obtained, and in particular, suppression of thickening of ink-jet ink containing the photocurable composition and liquid repellency with respect to the ink-jet nozzle can be obtained. This is preferable from the viewpoint of ejection stability. Moreover, if it is 2.0 mass% or less, it is preferable when maintaining high hardening sensitivity, without impairing the radical generation efficiency when using a radical photopolymerization initiator together.
  • a cationic initiator When a cationic initiator is used in combination with the photocurable composition of the present invention, it is desirable to use a cationic polymerization inhibitor together with a radical polymerization inhibitor from the viewpoint of improving storage stability.
  • the cationic polymerization inhibitor include alkali metal compounds, alkaline earth metal compounds, and amines.
  • Preferred amines as the cationic polymerization inhibitor include alkanolamines, N, N-dimethylalkylamines, N, N-dimethylalkenylamines, N, N-dimethylalkynylamines and the like.
  • triethanolamine triisopropanolamine, tributanolamine, N-ethyldiethanolamine, propanolamine, n-butylamine, sec-butylamine, 2-aminoethanol, 2-methylaminoethanol, 3-methylamino-1 -Propanol, 3-methylamino-1,2-propanediol, 2-ethylaminoethanol, 4-ethylamino-1-butanol, 4- (n-butylamino) -1-butanol, 2- (t-butylamino) ) Ethanol, N, N-dimethylundecanol, N, N-dimethyldodecanolamine, N, N-dimethyltridecanolamine, N, N-dimethyltetradecanolamine, N, N-dimethylpentadecanolamine N, N-dimethylnonadecylamine, N N-dimethylicosylamine,
  • the content of the cationic polymerization inhibitor in the photocurable composition of the present invention is preferably 0.001% by mass or more and 0.1% by mass or less with respect to the total mass of the photocurable composition.
  • the content is preferably 0.001% by mass or more, good storage stability of the photocurable composition is obtained, and in particular, suppression of thickening of the ink-jet ink containing the photocurable composition and good liquid repellency with respect to the ink-jet nozzle. It is preferable in that it can obtain the stability and can maintain the discharge stability.
  • it by setting it as 0.1 mass% or less, it becomes possible to fully maintain the acid generation efficiency at the time of using a photocation initiator together, and it is preferable when maintaining curing sensitivity.
  • the photocurable composition may further contain a coloring material as necessary.
  • the coloring material can be a dye or a pigment, but is preferably a pigment because it has good dispersibility with respect to the components of the ink and is excellent in weather resistance.
  • a pigment is not specifically limited, For example, the organic pigment or inorganic pigment of the following number described in a color index can be used.
  • the pigment for example, colorless inorganic pigments or colored organic pigments such as carbon black, titanium oxide, and calcium carbonate can be used.
  • organic pigment examples include insoluble azo pigments such as toluidine red, toluidine maroon, Hansa yellow, benzidine yellow, and pyrazolone red, soluble azo pigments such as lithol red, heliobordeaux, pigment scarlet, and permanent red 2B; alizarin, indanthrone, Derivatives from vat dyes such as thioindigo maroon; Phthalocyanine organic pigments such as phthalocyanine blue and phthalocyanine green; Quinacridone organic pigments such as quinacridone red and quinacridone magenta; Perylene organic pigments such as perylene red and perylene scarlet; Isoindolinone-based organic pigments such as linone yellow and isoindolinone orange; Pyranthrone-based organic pigments such as pyranthrone red and pyranthrone orange; Organic organic pigments, condensed azo organic pigments, benzimidazolone organic pigments, quinophthal
  • Organic pigments are exemplified below with color index (CI) numbers.
  • quinacridone-based, phthalocyanine-based, benzimidazolone-based, isoindolinone-based, condensed azo-based, quinophthalone-based, and isoindoline-based organic pigments are preferable because of excellent light resistance.
  • the organic pigment preferably has an average particle size in the ink of 10 nm or more and 150 nm or less as measured by laser scattering.
  • the average particle size of the pigment is less than 10 nm, a decrease in light resistance may occur due to a decrease in the particle size. If it exceeds 150 nm, it becomes difficult to maintain stable dispersion, and pigment precipitation is likely to occur. In particular, when used in an inkjet ink, the ejection stability is lowered, and there is a problem that minute mists called satellites are generated. Sometimes.
  • the average particle size is 150 nm or more and 300 nm or less, preferably 180 nm or more and 250 nm or less in order to provide whiteness and concealment.
  • coarse particles are removed by sufficient dispersion or filtration so that the maximum particle size of the pigment in the inkjet ink does not exceed 1.0 ⁇ m.
  • the ejection stability tends to be lowered.
  • the organic pigment can be refined by the following method. That is, a mixture composed of at least three components of an organic pigment, a water-soluble inorganic salt of 3 mass times or more of the organic pigment, and a water-soluble solvent is made into a clay, and is kneaded strongly with a kneader or the like to be refined, and then poured into water. Stir with a high speed mixer or the like to form a slurry. Next, filtration and washing of the slurry are repeated, and the water-soluble inorganic salt and the water-soluble solvent are removed by aqueous treatment. In the miniaturization step, a resin, a pigment dispersant and the like may be added.
  • water-soluble inorganic salts examples include sodium chloride and potassium chloride. These inorganic salts are used in the range of 3 to 20 times the mass of the organic pigment. After the dispersion treatment, chlorine ions (halogen ions) are washed with water in order to achieve the halogen ion content specified in the present invention. Perform the operation to remove. If the amount of the inorganic salt is less than 3 times by mass, a treated pigment having a desired size cannot be obtained, and if it is more than 20 times by mass, the washing process in the subsequent step is enormous, Processing amount is reduced.
  • the water-soluble solvent is not particularly limited as long as it is a solvent that can be used for making an appropriate clay state of an organic pigment and a water-soluble inorganic salt used as a crushing aid and performing sufficient crushing efficiently, and is soluble in water.
  • a high boiling point solvent having a boiling point of 120 to 250 ° C. is preferable from the viewpoint of safety.
  • the surface treatment by a known technique such as an acid treatment or a basic treatment, a synergist, or various coupling agents ensures the dispersion stability. Therefore, it is preferable.
  • the pigment is 1.5 to 8% by mass in the case of a color excluding white in the photocurable composition, and 10 to 30% in the case of a white ink using titanium oxide. % Is preferably included.
  • Pigment dispersant It is preferable to contain a pigment dispersant for dispersing the above-described pigment in the photocurable composition.
  • the pigment dispersant include a hydroxyl group-containing carboxylic acid ester, a salt of a long chain polyaminoamide and a high molecular weight acid ester, a salt of a high molecular weight polycarboxylic acid, a salt of a long chain polyaminoamide and a polar acid ester, a high molecular weight unsaturated acid ester, Polymer copolymer, modified polyurethane, modified polyacrylate, polyether ester type anionic activator, naphthalene sulfonic acid formalin condensate salt, aromatic sulfonic acid formalin condensate salt, polyoxyethylene alkyl phosphate ester, polyoxyethylene nonyl Examples thereof include phenyl ether, stearylamine acetate, and pigment derivatives.
  • Anti-Terra-U polyaminoamide phosphate
  • Anti-Terra-203 / 204 high molecular weight polycarboxylate
  • Disbyk-101 polyaminoamide phosphate manufactured by BYK Chemie.
  • Salt (acid ester), 107 (hydroxyl group-containing carboxylic acid ester), 110 (copolymer containing acid group), 130 (polyamide), 161, 162, 163, 164, 165, 166, 170 (polymer copolymer) ) "," 400 ",” Bykumen "(high molecular weight unsaturated acid ester),” BYK-P104, P105 (high molecular weight unsaturated acid polycarboxylic acid) ",” P104S, 240S (high molecular weight unsaturated acid polycarboxylic acid) And silicone) ”,“ Lactimon (long chain amine and unsaturated acid polycarboxylic acid) Silicone) "and the like.
  • Demol RN N (Naphthalenesulfonic acid formalin condensate sodium salt), MS, C, SN-B (aromatic sulfonic acid formalin condensate sodium salt), EP”, “Homogenol L-18” manufactured by Kao Corporation.
  • These pigment dispersants are preferably contained in an amount of 5 to 70% by mass, preferably 10 to 50% by mass, based on the pigment 100.
  • the content is less than 5%, dispersion stability may be difficult to obtain.
  • the content is more than 70%, for example, when used for inkjet ink, the ejection stability may deteriorate.
  • these pigment dispersants have a solubility of 5% by mass or more in the entire photocurable composition at 0 ° C.
  • solubility is less than 5% by mass, an undesired polymer gel or pigment soft aggregate may be generated when the photocurable composition is stored at a low temperature between about 0 ° C. and 10 ° C. While the storage stability of a photocurable composition deteriorates, when it uses for an inkjet ink, discharge stability may deteriorate.
  • Organic solvent A small amount of a solvent such as an alcohol solvent, an ester solvent, an ether solvent, an ether ester solvent, a ketone solvent, an aromatic hydrocarbon solvent, or a nitrogen-containing organic solvent may be contained. In addition, it is preferable that it is 0.2 to 5 mass% with respect to the mass of the whole photocurable composition as content of an organic solvent from a viewpoint of photocurability or an environment.
  • the content of the organic solvent from the viewpoint of the environment.
  • the curability can be improved, while the influence of curing shrinkage becomes significant.
  • curing shrinkage can be suppressed while maintaining adhesion by containing a metal chelate compound even when curing shrinkage occurs more remarkably when the content of the organic solvent is reduced.
  • the photocurable composition of the present invention is used for the purpose of improving emission stability, print head and ink packaging container compatibility, storage stability, image storage stability, and other various performances as necessary.
  • additives for example, surfactants, lubricants, fillers, antifoaming agents, gelling agents, thickeners, specific resistance adjusting agents, film forming agents, ultraviolet absorbers, antioxidants, fading Inhibitors, antifouling agents, rust inhibitors and the like can be appropriately selected and used.
  • surfactants that can be used in the photocurable composition of the present invention include anionic surfactants such as dialkylsulfosuccinates, alkylnaphthalenesulfonates, fatty acid salts, polyoxyethylene alkyl ethers, Nonionic surfactants such as polyoxyethylene alkyl allyl ethers, acetylene glycols, polyoxyethylene / polyoxypropylene block copolymers, cationic surfactants such as alkylamine salts and quaternary ammonium salts, silicone-based Fluorine-type surfactant is mentioned, Silicone-type or fluorine-type surfactant is especially preferable.
  • anionic surfactants such as dialkylsulfosuccinates, alkylnaphthalenesulfonates, fatty acid salts, polyoxyethylene alkyl ethers
  • Nonionic surfactants such as polyoxyethylene alkyl allyl ethers, acetylene glycols, polyoxy
  • a silicone-based or fluorine-based surfactant By adding a silicone-based or fluorine-based surfactant, it is possible to further suppress ink mixing on recording media made of various hydrophobic resins such as vinyl chloride sheets and recording media that absorb slowly such as printing paper. And high-quality printed images can be obtained.
  • the surfactant is particularly preferably used in combination with the low surface tension water-soluble organic solvent.
  • the silicone-based surfactant is preferably a polyether-modified polysiloxane compound.
  • KF-351A, KF-642, X-22-4272 manufactured by Shin-Etsu Chemical Co., Ltd., BYK307, BYK345, BYK347 manufactured by Big Chemie, BYK348, TSF4452 manufactured by Toshiba Silicone Co., etc. can be mentioned.
  • Fluorosurfactant means a substance obtained by substituting part or all of it with fluorine instead of hydrogen bonded to carbon of a hydrophobic group of a normal surfactant. Of these, those having a perfluoroalkyl group in the molecule are preferred.
  • fluorosurfactants some are from DIC under the trade name Megafac F and from Asahi Glass under the trade name Surflon, Minnesota Mining and Manufacturing Company Under the trade name Fluorad FC from the company, under the trade name Monflor from Imperial Chemical Industry, and under the trade name Zonyls from EI Dupont Nemeras & Company, Alternatively, they are commercially available from Rubevelke Hoechst under the trade name Licobet VPF and from Neos under the trade name Fantage.
  • the addition amount of the surfactant is preferably 0.001% by mass or more and less than 1.0% by mass with respect to the total mass of the photocurable composition.
  • a gelling agent can be added to the photocurable composition of the present invention from the viewpoint of improving curability and adhesion.
  • the addition amount of the gelling agent is that the photocurable composition is gelated (sol-gel phase transition due to temperature change) and from the viewpoint that it can be sufficiently dissolved in the photocurable composition.
  • 0.5 mass% or more and 10 mass% or less are preferable with respect to mass, More preferably, they are 1 mass% or more and 10 mass% or less.
  • the gelling agent is present in the photocurable composition and thickens or gels the photocurable composition of the present invention.
  • a gelling agent having a function of reversibly sol-gel phase transition of the photocurable composition depending on temperature can be used.
  • sol-gel transition temperature of the photocurable composition can be arbitrarily set.
  • “Sol-gel phase transition temperature” refers to the temperature at the transition (transition) point from the sol state to the gel state (transition), and is called the gel transition temperature, gel dissolution temperature, gel softening temperature, and sol-gel transition point gelation point. Is synonymous with the term used.
  • the gelling agent include aliphatic ketone compounds (dialkyl ketones), fatty acid ester compounds, higher fatty acids, higher alcohols (fatty acid alcohols), fatty acid amides, oil gelling agents, and the like.
  • the above-described gelling agent can also be suitably used for inkjet inks containing a photocurable composition.
  • the temperature is preferably in the range of 30 to 100 ° C. from the viewpoints of, for example, stable emission of ink droplets and adverse effects associated with high-temperature heating.
  • the sol-gel transition temperature is preferably between the ink temperature in the ink jet recording head and the temperature of the recording medium.
  • gelling agent improves nail scratch resistance. Since the gelling agent thickens the ink, it inhibits the molecular movement of the monomer and promotes the coordinate bond between the EO chain and the metal chelate, which increases the degree of cross-linking of the film and improves nail scratch resistance. Yes.
  • Examples of the aliphatic ketone compound include dibehenyl ketone (carbon number: 21-22), distearyl ketone (carbon number: 17-18), dipalmityl ketone (carbon number: 15-16), dimyristyl ketone ( Carbon number: 13-14), palmityl stearyl ketone (carbon number: 15-18), stearyl behenyl ketone (carbon number: 17-22) and the like are included.
  • the carbon number in the said parenthesis represents the carbon number of each of the two hydrocarbon groups divided by a carbonyl group.
  • Examples of aliphatic ester compounds include behenyl behenate (carbon number: 21-22), stearyl stearate (carbon number: 17-18), cetyl palmitate (carbon number: 15-15), palmitic acid stearate (carbon). Number: 17-16), myristyl myristate (carbon number: 13-14), myristyl cellolate (carbon number: 25-30), behenyl montanate (carbon number: 24-22), and the like.
  • the number of carbons in the parenthesis represents the number of carbons of each of the two hydrocarbon groups that are divided by the ester group.
  • higher fatty acids examples include behenic acid (carbon number: 21), arachidic acid (carbon number: 19), stearic acid (carbon number: 17), palmitic acid (carbon number: 15), oleic acid (carbon number: 17). ), Erucic acid (carbon number: 21), and the like.
  • fatty acid alcohols examples include stearyl alcohol (carbon number: 17) and behenyl alcohol (carbon number: 21).
  • fatty acid amides examples include stearic acid amide (carbon number: 17), behenic acid amide (carbon number: 21), oleic acid amide (carbon number: 17), erucic acid amide (carbon number: 21) and ricinoleic acid amide ( Fatty acid amides such as carbon number: 17) are included.
  • the viscosity at 25 ° C. of the photocurable composition is preferably 10 mPa ⁇ s or more and 500 mPa ⁇ s or less from the viewpoint of handling such as ease of spreading when the photocurable composition is applied with a bar coater or the like.
  • the surface tension can be appropriately adjusted and used according to the recording medium to be coated.
  • the gelling agent which makes a sol-gel phase transition by temperature change is contained, it is preferable to apply with a bar coater or the like above the sol-gel phase transition temperature.
  • the viscosity at the coating temperature is preferably 10 mPa ⁇ s or more and 500 mPa ⁇ s or less from the viewpoint of handling.
  • the heating conditions and the heating time can be appropriately adjusted.
  • a metal chelate compound, a photopolymerizable compound, or the like is placed in a stainless beaker and heated on a 65 ° C. hot plate. It can be prepared and used by heating and stirring and dissolving for 1 hour while heating.
  • a photocurable inkjet ink can also be obtained by using the photocurable composition obtained here.
  • the surface tension of the photocurable inkjet ink in the present invention is 15 mN / m or more, so that the periphery of the nozzle of the inkjet head does not get wet and the discharge capacity does not decrease, and the surface energy is less than 35 mN / m. This is preferable because the coated paper or resin recording medium which is lower than normal paper does not wet well and does not cause whitening.
  • the surface tension of the photocurable ink-jet ink can be determined by the Wilhelmy method (plate method).
  • the surface tension of the photocurable ink-jet ink can be adjusted by selecting the photocurable compound described above, adjusting the blending ratio, and adding the surfactant described above.
  • the physical properties of the photocurable inkjet ink of the present invention preferably have the same physical properties as those of a normal photocurable inkjet ink. That is, the viscosity is 2 mPa ⁇ s or more and 50 mPa ⁇ s or less at 25 ° C., and the ink temperature at the time of ejection is 20 ° C. or more and less than 100 ° C., preferably 25 ° C. or more and 60 ° C. or less.
  • the ink is preferably ejected at an ink temperature such that the ink viscosity is 7 mPa ⁇ s or more and 15 mPa ⁇ s or less, more preferably 8 mPa ⁇ s or more and 13 mPa ⁇ s or less.
  • the viscosity of the inkjet ink can be determined by a rotational viscometer.
  • the viscosity of the inkjet ink can be adjusted by selecting the above-mentioned photopolymerizable compound and adjusting the blending ratio.
  • the photocurable inkjet ink contains a gelling agent that undergoes a sol-gel phase transition by temperature change, it is preferable if the viscosity at the time of emission satisfies a physical property value of 3 mPa ⁇ s to 20 mPa ⁇ s. Can be used.
  • the ink is free from corrosion.
  • the continuous type it is necessary to adjust the electric conductivity with the electrolyte. In this case, it may be necessary to adjust the electric conductivity to 0.5 mS / cm or more.
  • the electric conductivity of the ink-jet ink can be determined by immersing two electrodes separated by a certain distance in the ink, applying a certain voltage between both electrodes, and measuring the value of the current flowing between the electrodes.
  • the electrical conductivity of the inkjet ink can be adjusted by the selection and blending ratio of the above-described photopolymerizable compound, polymerization initiator, and sensitizer, and the water content of the inkjet ink.
  • a more preferable form is that when the DSC (Differential Scanning Calorimetry) measurement of the ink is performed in the range from 25 ° C. to ⁇ 25 ° C. at a rate of 5 ° C. per minute, the unit The exothermic amount per mass is not 10 mJ / mg or more.
  • DSC Different Scanning Calorimetry
  • an inkjet ink containing the photocurable composition as the photocurable composition will be described in detail as a specific example, but it goes without saying that the scope of the present invention is not limited to the inkjet ink.
  • the inkjet ink of the present invention is a photopolymerizable compound that is a photocurable compound, a photoinitiator, a pigment dispersant in the case of using a pigment as a coloring material, and a pigment, and a normal dispersing machine such as a sand mill. It is preferable to be manufactured by dispersing well. It is preferable to prepare a concentrated liquid with a high concentration of pigment in advance and dilute with a photopolymerizable compound. Sufficient dispersion is possible even with dispersion by ordinary dispersers.
  • the prepared ink is preferably filtered through a filter having a pore diameter of 3 ⁇ m or less, and more preferably 1 ⁇ m or less.
  • [recoding media] As a recording medium used in a recording method using the photocurable composition of the present invention and a recording method using a photocurable inkjet ink, all of a wide range of synthetic resins conventionally used in various applications are targeted. Specific examples include polyester, polyvinyl chloride, polyethylene, polyurethane, polypropylene, acrylic resin, polycarbonate, polystyrene, acrylonitrile-butadiene-styrene copolymer, polyethylene terephthalate, polybutadiene terephthalate, and the like. The thickness and shape of the substrate are not limited at all. In particular, polypropylene, polyethylene, and polyethylene terephthalate are preferable as the recording medium for the photocurable inkjet ink of the present invention. In addition, metals, glass, papers (for example, printing paper), etc. can be used.
  • the recording medium used in the invention may be subjected to surface treatment as necessary.
  • the surface treatment includes corona treatment, plasma treatment, excimer treatment and the like.
  • an active site capable of interacting with a metal chelate compound such as an OH group is generated on the surface of the recording medium, so that the surface adhesion of the recording medium is further improved.
  • polyvinyl chloride which is one of the recording media used in the ink jet recording method of the present invention, include SOL-371G, SOL-373M, SOL-4701 (manufactured by Big Technos Co., Ltd.), glossy PVC (Co., Ltd.).
  • the following various base materials are used as constituent elements, and one kind of base material is used alone, or a plurality of kinds are used. These substrates can be used in combination.
  • the resin base material containing no plasticizer used in the present invention include ABS resin, polycarbonate (PC) resin, polyacetal (POM) resin, polyamide (PA) resin, polyethylene terephthalate (PET) resin, and polyimide (PI).
  • the resin base material containing no plasticizer used in the present invention include ABS resin, polycarbonate (PC) resin, polyacetal (POM) resin, polyamide (PA) resin, polyethylene terephthalate (PET) resin, and polyimide (PI).
  • examples thereof include a resin, an acrylic resin, a polyethylene (PE) resin, a polypropylene (PP) resin, and a hard polyvinyl chloride (PVC) resin that does not contain a plasticizer.
  • These resins are characterized by not containing a plasticizer, but there are no particular restrictions on other properties such as thickness, shape, color, softening temperature, and hardness.
  • the recording medium used in the present invention is preferably ABS resin, PET resin, PC resin, POM resin, PA resin, PI resin, hard PVC resin not containing plasticizer, acrylic resin, PE resin, or PP resin. More preferred are ABS resin, PET resin, PC resin, PA resin, hard PVC resin not containing plasticizer, and acrylic resin.
  • non-absorbing inorganic base material used in the present invention examples include a glass plate, a metal plate such as iron or aluminum, and a ceramic plate. These inorganic substrates are characterized by not having an ink-absorbing layer on the surface. These non-absorbing inorganic base materials are not particularly limited with respect to other properties such as thickness, shape, color, softening temperature, and hardness.
  • the photocurable inkjet ink of the present invention can exhibit the effects of the present invention particularly well in a recording medium having a surface energy of 25 mN / m or more and less than 60 mN / m.
  • the surface energy of the recording medium according to the present invention can be calculated by measuring the contact angle using three or more liquids with known surface tensions.
  • the photocurable composition As a recording method using the photocurable composition, the photocurable composition is applied to a recording medium, and then irradiated with actinic rays such as ultraviolet rays to cure the curable composition.
  • actinic rays such as ultraviolet rays
  • Commonly used coating methods include bar coating, spray coating, curtain coating, roll coating, screen printing, offset printing, and gravure printing.
  • the primer layer, the image, and the overcoat layer can be formed by the above-described method.
  • the photocurable ink-jet ink is ejected onto the recording medium from the ink jet nozzle, and then an active ray such as ultraviolet ray is irradiated onto the coating film on the recording medium.
  • a recording method for curing the ink can be used.
  • the ink-jet head used in the in-jet recording method of the present invention for forming an image by ejecting a photocurable ink-jet ink may be an on-demand system or a continuous system.
  • Discharge methods include electro-mechanical conversion methods (eg, single cavity type, double cavity type, bender type, piston type, shear mode type, shared wall type, etc.), electro-thermal conversion methods (eg, thermal ink jet) Any ejection method such as a mold, a bubble jet (registered trademark) mold, or the like may be used.
  • the active energy ray is preferably irradiated for 0.001 second or more and 1.0 second or less after ink landing, more preferably 0.001 as the irradiation condition of the active energy ray. 2 seconds or more and 0.5 seconds or less.
  • the irradiation timing is as early as possible.
  • the irradiation method of the active energy ray is not particularly limited, and can be performed by the following method, for example.
  • a light source is provided on both sides of the head unit described in JP-A-60-132767, and the head and the light source are scanned by a shuttle method. Irradiation is performed after a certain period of time after ink landing, and is accompanied by driving.
  • a method for completing the curing by using another light source a method using an optical fiber described in US Pat. No. 6,145,979, or a collimated light source is applied to a mirror surface provided on the side surface of the head unit, to the recording unit A method of irradiating ultraviolet rays can be given.
  • the irradiation of active energy rays is divided into two stages.
  • the active energy rays are irradiated by the above-described method within 0.001 second to 2.0 seconds after ink landing, and after all printing is completed, further activation is performed.
  • a method of irradiating energy rays is also a preferred embodiment.
  • the total ink film thickness after ink landing is 2 ⁇ m or more and 20 ⁇ m or less. This is preferable from the viewpoint of suppressing inconveniences to the appearance and texture, such as changes in the texture of the medium.
  • the “total ink film thickness” here means the maximum value of the film thickness of the ink drawn on the recording medium, and even for a single color, other two color layers (secondary colors), three color layers, Even when recording is performed using a four-color overlapping (white ink base) inkjet recording method, the meaning of the total ink film thickness is the same.
  • the heating temperature is preferably 35 ° C. or higher and 100 ° C. or lower, and more preferably irradiated with active energy rays while being kept at 35 ° C. or higher and 80 ° C. or lower in view of ejection stability.
  • an ink supply system such as an ink tank constituting a head carriage, a supply pipe, a front chamber ink tank immediately before the head, a pipe with a filter
  • a piezo head or the like is insulated and heated to a predetermined temperature by a panel heater, a ribbon heater, warm water or the like.
  • the control range of the ink temperature is preferably set temperature ⁇ 5 ° C., more preferably set temperature ⁇ 2 ° C., and particularly preferably set temperature ⁇ 1 ° C. from the viewpoint of ejection stability.
  • the amount of liquid droplets discharged from each nozzle is preferably 2 pL or more and 20 pL or less from the viewpoint of recording speed and image quality.
  • FIG. 1 is a front view showing a configuration of a main part of the recording apparatus.
  • the recording apparatus 1 includes a head carriage 2, a recording head 3, an irradiation unit 4, a platen unit 5, and the like.
  • the platen unit 5 is installed under the recording medium P.
  • the platen portion (recording medium support member) 5 has a function of absorbing ultraviolet rays and absorbs excess ultraviolet rays that have passed through the recording medium P. As a result, a high-definition image can be reproduced very stably.
  • the recording medium P is guided by the guide member 6 and moves from the near side to the far side in FIG. 1 by the operation of the conveying means (not shown).
  • a head scanning unit (not shown) scans the recording head 3 held by the head carriage 2 by reciprocating the head carriage 2 in the Y direction in FIG.
  • the head carriage 2 is installed on the upper side of the recording medium P, and accommodates a plurality of recording heads 3 to be described later according to the number of colors used for image printing on the recording medium P, and arranges discharge ports on the lower side.
  • the head carriage 2 is installed with respect to the main body of the recording apparatus 1 in such a manner that it can reciprocate in the Y direction in FIG. 1, and reciprocates in the Y direction in FIG. 1 by driving the head scanning means.
  • the head carriage 2 is white (W), yellow (Y), magenta (M), cyan (C), black (K), light yellow (Ly), light magenta (Lm), and light cyan (Lc).
  • the recording head 3 for light black (Lk) and white (W) is drawn.
  • the number of colors of the recording head 3 stored in the head carriage 2 is appropriately determined. Is.
  • the recording head 3 is directed from the discharge port toward the recording medium P by the operation of a plurality of discharge means (not shown) provided inside the photocurable inkjet ink supplied by the ink supply means (not shown). To discharge.
  • the recording head 3 is a certain area (landing possible area) in the recording medium P during the scanning in which the recording head 3 moves from one end of the recording medium P to the other end of the recording medium P in the Y direction in FIG.
  • the photocurable inkjet ink is ejected as ink droplets, and the ink droplets are landed on the landable area.
  • the above scanning is performed as many times as necessary, and after the photocurable inkjet ink is ejected toward one landable area, the recording medium P is appropriately moved from the front to the back in FIG. While performing the scanning by the means, the recording head 3 discharges the photocurable inkjet ink to the next landable area adjacent to the rearward direction in FIG.
  • the irradiation means 4 includes a light source 8, for example, an ultraviolet lamp that emits ultraviolet light in a specific wavelength region with stable exposure energy, and a filter that transmits ultraviolet light of a specific wavelength.
  • a light source 8 for example, an ultraviolet lamp that emits ultraviolet light in a specific wavelength region with stable exposure energy, and a filter that transmits ultraviolet light of a specific wavelength.
  • the ultraviolet lamp a mercury lamp, a metal halide lamp, an excimer laser, an ultraviolet laser, a cold cathode tube, a hot cathode tube, a black light, an LED (light emitting diode), etc.
  • Cathode tubes, hot cathode tubes, mercury lamps or black lights are preferred, and LEDs are particularly preferred because of their long life and low cost.
  • the irradiation means 4 for curing the ultraviolet ink can be produced at low cost.
  • an LED is a single wavelength light source, and its illuminance tends to be lower than a light source having a plurality of emission line spectra such as a high-pressure mercury lamp.
  • a light source having a plurality of emission line spectra such as a high-pressure mercury lamp.
  • the illuminance is preferably 8 W / cm 2 or less, and more preferably 2 W / cm 2 or less.
  • the irradiating means 4 is the maximum one that can be set by the recording apparatus (photocurable ink jet printer) 1 among the landable areas in which the recording head 3 ejects the photocurable ink jet ink by one scan driven by the head scanning means.
  • the shape is substantially the same as or larger than the landable area.
  • the irradiation means 4 is fixed on both sides of the head carriage 2 so as to be substantially parallel to the recording medium P.
  • the ink discharge of the recording head 3 is determined from the distance h1 between the irradiation means 4 and the recording medium P. It is effective to increase the distance h2 between the portion 31 and the recording medium P (h1 ⁇ h2), or to increase the distance between the recording head 3 and the irradiation means 4 (to increase the distance).
  • the wavelength of the ultraviolet rays irradiated by the irradiation means 4 can be changed as appropriate by replacing the ultraviolet lamp or filter provided in the irradiation means 4.
  • FIG. 2 is a top view showing another example of the configuration of the main part of the ink jet recording apparatus.
  • the ink jet recording apparatus shown in FIG. 2 is called a line head system, and a plurality of recording heads 3 of each color are fixedly arranged on the head carriage 2 so as to cover the entire width of the recording medium P. Yes.
  • the entire width of the recording medium P is also covered so as to cover the entire area of the ink printing surface.
  • Irradiation means 4 arranged so as to cover is provided.
  • the ultraviolet lamp used for the irradiation means 4 can be the same as that described in FIG.
  • the head carriage 2 and the irradiating means 4 are fixed, and only the recording medium P is transported to perform image formation by ejecting ink and curing.
  • a layer made of a photocurable composition such as a primer layer or an overcoat layer can be formed on a recording medium using an inkjet recording apparatus.
  • a photocurable composition that does not contain a colorant such as a pigment is discharged from an inkjet head, and the discharged photocurable composition is cured by irradiating with ultraviolet rays or the like. Can be formed.
  • an image after forming the above-described primer layer, an image can be formed by ejecting an inkjet ink containing a coloring material such as a pigment to form a high-quality image even on a non-absorbing medium, for example. It is possible to form an image with high adhesion while suppressing curing shrinkage.
  • a photocurable composition that does not contain a coloring material such as a pigment is discharged from an inkjet head, and the discharged photocurable composition is irradiated with ultraviolet light or the like. It is formed by irradiating and curing. In this case, it is possible to provide an overcoat layer that can adhere well to the formed image and can suppress curing shrinkage.
  • a colored primer layer or an overcoat layer may be formed by adding a color material such as a pigment to the photocurable composition.
  • samples (photocurable compositions) 1 to 22 were prepared according to the compositions described in Tables 1 and 2.
  • the photocurable composition was prepared by first preparing the photopolymerizable compounds (A) to (D), the metal chelate compounds (A) to (G), the intramolecular cleavage type initiator, the hydrogen abstraction type initiator, etc. And it was made to contain according to Table 2, and it was made to melt
  • a coating film of the photocurable composition was formed by a bar coating method.
  • Each of the above-prepared samples 1 to 22 was subjected to white PET # 50 (manufactured by Maru Adhesive Co., Ltd.) having a width of 75 mm and a length of 130 mm, a corona-treated biaxially stretched polypropylene film OPP (manufactured by Okamoto), and YUPO (Yupo) using a bar coater.
  • the film was uniformly applied to a thickness of 10 ⁇ m. After the application, it was cured with an LED lamp (8 W / cm 2 , water cooled unit) manufactured by Phoseon Technology.
  • adhesive tape (Scotch # 250, manufactured by Sumitomo 3M) is attached to the cured composition sample obtained by the cross-cut tape peel residual adhesion test (JIS K 5400 cross-cut test) and reciprocated once with a 2 kg roller. After the crimping, it was peeled off at once, the number of remaining grid-like samples was investigated, and the adhesion rate was evaluated according to the following rank, which was taken as one of the adhesion indexes. ⁇ or more is a practically favorable range.
  • Adhesion residual rate 80% or more 100%
  • ⁇ There is no warpage in the cured product. ⁇ : Warping is observed in the cured product, but within the allowable range.
  • SR230 Diethylene glycol diacrylate
  • Pigment dispersion 1 Pigment Black 7 (Mitsubishi Chemical Corporation, # 52)
  • Samples (ink compositions) 23 to 32 of the inkjet ink composition described in Table 3 were prepared.
  • photopolymerizable compounds (A) to (C), a metal chelate compound (D), an intramolecular cleavage type initiator, a hydrogen abstraction type initiator, and the like are contained according to Table 3, and 65 ° C.
  • the sample was dissolved on a hot plate while stirring with heating.
  • the crosslinking accelerator (A) was also contained as needed.
  • the pigment dispersion prepared by the above procedure was added and adjusted by stirring.
  • the obtained ink composition was filtered through a Teflon (registered trademark) 3 ⁇ m membrane filter manufactured by ADVATEC.
  • the ink supply system was composed of an ink tank, a supply pipe, a sub-ink tank immediately before the head, a pipe with a filter, and a piezo head.
  • the entire tank was heated from the tank to the head portion and heated at 100 ° C.
  • the piezo head applied a voltage so as to form a droplet of 2 pl, and ejected it using four heads each having a resolution of 360 dpi to form a 1440 ⁇ 1440 dpi K single-color solid image.
  • adhesive tape (Scotch # 250, manufactured by Sumitomo 3M) is attached to the cured composition sample obtained by the cross-cut tape peel residual adhesion test (JIS K 5400 cross-cut test) and reciprocated once with a 2 kg roller. After the crimping, it was peeled off at once, the number of remaining grid-like samples was investigated, and the adhesion rate was evaluated according to the following rank, which was taken as one of the adhesion indexes. ⁇ or more is a practically favorable range.
  • Adhesion residual rate 80% or more 100%
  • ⁇ There is no warpage in the cured product. ⁇ : Warping is observed in the cured product, but within the allowable range.
  • samples (photocurable compositions) 33 to 39 were prepared according to the compositions shown in Table 4.
  • the photocurable composition is prepared by first preparing the photopolymerizable compounds (A) to (L), the metal chelate compound (D), the crosslinking accelerator (A), the intramolecular cleavage type initiator, the hydrogen abstraction type initiator, Surfactants and the like were contained according to Table 4 and dissolved while heating and stirring on a 65 ° C. hot plate.
  • a coating film of the photocurable composition was formed by a bar coating method.
  • Each of the prepared samples 33 to 39 was prepared by using a bar coater with a white PET # 50 (manufactured by Maru Adhesive Co., Ltd.) having a width of 75 mm and a length of 130 mm, a corona-treated biaxially oriented polypropylene film OPP (manufactured by Okamoto), It was uniformly applied to an axially stretched polypropylene film OPP (manufactured by Okamoto) and YUPO (manufactured by Yupo) so as to have a thickness of 10 ⁇ m. After the application, it was cured with an LED lamp (8 W / cm 2 , water cooled unit) manufactured by Phoseon Technology.
  • adhesive tape (Scotch # 250, manufactured by Sumitomo 3M) is attached to the cured composition sample obtained by the cross-cut tape peel residual adhesion test (JIS K 5400 cross-cut test) and reciprocated once with a 2 kg roller. After the crimping, it was peeled off at once, the number of remaining grid-like samples was investigated, and the adhesion rate was evaluated according to the following rank, which was taken as one of the adhesion indexes. ⁇ or more is a practically favorable range.
  • Adhesion residual rate 80% or more 100%
  • ⁇ There is no warpage in the cured product. ⁇ : Warping is observed in the cured product, but within the allowable range.
  • Samples (ink compositions) 40 to 46 of the inkjet ink composition described in Table 5 were prepared.
  • the ink composition is prepared by first preparing the photopolymerizable compounds (A) to (L), the metal chelate compound (D), the gelling agents (A) to (C), the intramolecular cleavage type initiator, and the hydrogen abstraction type start. Agents, surfactants, and the like were added according to Table 5 and dissolved on a 65 ° C. hot plate with heating and stirring. Moreover, the crosslinking accelerator (A) was also contained as needed. Then, after that, the pigment dispersion prepared by the above procedure was added and adjusted by stirring. The obtained ink composition was filtered through a Teflon (registered trademark) 3 ⁇ m membrane filter manufactured by ADVATEC.
  • ⁇ Inkjet image forming method Each sample 40 to 46 prepared above was loaded into an ink jet recording apparatus having a recording head equipped with a piezo ink jet nozzle, and a long white PET # 50 (manufactured by Maru Adhesion Co., Ltd.) having a width of 600 mm and a length of 500 m, corona Image recording was continuously performed on the treated biaxially stretched polypropylene film OPP (manufactured by Okamoto), Yupo, in the following manner. The conveyance speed of the recording material was 30 m / s.
  • the ink supply system was composed of an ink tank, a supply pipe, a sub-ink tank immediately before the head, a pipe with a filter, and a piezo head.
  • the entire tank was heated from the tank to the head portion and heated at 100 ° C.
  • the piezo head applied a voltage so as to form a droplet of 2 pl, and ejected it using four heads each having a resolution of 360 dpi to form a 1440 ⁇ 1440 dpi K single-color solid image.
  • adhesive tape (Scotch # 250, manufactured by Sumitomo 3M) is attached to the cured composition sample obtained by the cross-cut tape peel residual adhesion test (JIS K 5400 cross-cut test) and reciprocated once with a 2 kg roller. After the crimping, it was peeled off at once, the number of remaining grid-like samples was investigated, and the adhesion rate was evaluated according to the following rank, which was taken as one of the adhesion indexes. ⁇ or more is a practically favorable range.
  • Adhesion residual rate 80% or more 100%
  • ⁇ There is no warpage in the cured product. ⁇ : Warping is observed in the cured product, but within the allowable range.
  • ⁇ No effect on the cured product ⁇ : Slightly scratched on the cured product, but within the allowable range ⁇ : NG level at which the cured product is severely scratched or the image peels off
  • the photocurable composition of the present invention and the photocurable inkjet ink containing the photocurable composition are suitable for forming an image on a recording medium, particularly a non-absorbing recording medium.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Medicinal Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Ink Jet Recording Methods And Recording Media Thereof (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Ink Jet (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polymerisation Methods In General (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

L'invention concerne une composition photodurcissable contenant un composé photopolymérisable et un photo-initiateur, le composé photopolymérisable étant un monomère polymérisable par voie radicalaire et le photo-initiateur étant un initiateur photoradicalaire. La composition photodurcissable est caractérisée en ce qu'elle contient en outre un composé chélate métallique, dans lequel l'élément métallique central dans le composé chélate métallique est choisi parmi les éléments métalliques appartenant au groupe 2, au groupe 4, au groupe 8 et au groupe 13 et le composé chélate métallique est contenu dans une quantité de 0,1 à 5 % en masse inclus par rapport à la masse totale de la composition photodurcissable. Ainsi, il devient possible de procurer : une composition photodurcissable qui présente une adhésivité prolongée et ne subit pas de rétrécissement lors du durcissement; et une encre photodurcissable pour jet d'encre.
PCT/JP2015/058252 2014-03-31 2015-03-19 Composition photodurcissable et encre photodurcissable pour jet d'encre la contenant, procédé d'enregistrement utilisant la composition photodurcissable, et procédé d'enregistrement utilisant l'encre photodurcissable pour jet d'encre WO2015151833A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
JP2016511530A JP6536570B2 (ja) 2014-03-31 2015-03-19 光硬化性組成物、及びそれを含有する光硬化性インクジェットインク、光硬化性組成物を用いた記録方法、並びに光硬化性インクジェットインクを用いた記録方法
US15/127,636 US10011665B1 (en) 2014-03-31 2015-03-19 Photocurable composition and photocurable inkjet ink containing same, recording method using photocurable composition, and recording method using photocurable inkjet ink

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2014-074029 2014-03-31
JP2014074029 2014-03-31

Publications (1)

Publication Number Publication Date
WO2015151833A1 true WO2015151833A1 (fr) 2015-10-08

Family

ID=54240164

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2015/058252 WO2015151833A1 (fr) 2014-03-31 2015-03-19 Composition photodurcissable et encre photodurcissable pour jet d'encre la contenant, procédé d'enregistrement utilisant la composition photodurcissable, et procédé d'enregistrement utilisant l'encre photodurcissable pour jet d'encre

Country Status (3)

Country Link
US (1) US10011665B1 (fr)
JP (1) JP6536570B2 (fr)
WO (1) WO2015151833A1 (fr)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017066348A (ja) * 2015-10-02 2017-04-06 東洋インキＳｃホールディングス株式会社 活性エネルギー線硬化型印刷インキおよび印刷物
JP2019073631A (ja) * 2017-10-17 2019-05-16 三菱エンジニアリングプラスチックス株式会社 樹脂組成物および成形品
JP2019178287A (ja) * 2018-03-30 2019-10-17 太陽インキ製造株式会社 インクジェット印刷用の硬化性組成物、その硬化物及びその硬化物を有する電子部品
CN111886300A (zh) * 2018-03-30 2020-11-03 太阳油墨制造株式会社 喷墨印刷用的固化性组合物、其固化物和具有该固化物的电子部件
JP2020533451A (ja) * 2017-09-10 2020-11-19 マンキーヴィッチ ゲブリューダー ウント コンパニー （ゲーエムベーハー ウント コンパニー カーゲー）Ｍａｎｋｉｅｗｉｃｚ Ｇｅｂｒ． ＆ Ｃｏ． ＧｍｂＨ＆ Ｃｏ． ＫＧ 再生利用可能なコーティング及び再使用可能なプラスチックに印刷するためのその使用
JP2021509924A (ja) * 2018-01-09 2021-04-08 サン・ケミカル・コーポレーション 第ｉｖ族金属キレート、ならびに放射線硬化性インクおよびコーティング組成物におけるその使用
US11193028B2 (en) * 2015-11-16 2021-12-07 Ricoh Company, Ltd Active-energy-ray-curable composition, active-energy-ray-curable ink, composition stored container, two-dimensional or three-dimensional image forming method, two-dimensional or three-dimensional image forming apparatus, and processed product

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10703114B2 (en) * 2018-06-15 2020-07-07 Ricoh Company, Ltd. Printing device and printing method
KR20230062597A (ko) * 2020-09-02 2023-05-09 카티바, 인크. 잉크젯 프린터 제어 방법

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62101670A (ja) * 1985-10-29 1987-05-12 Touka Shikiso Kagaku Kogyo Kk 紫外線硬化型印刷インキ用ゲルワニス
JPH05119201A (ja) * 1991-10-28 1993-05-18 Olympus Optical Co Ltd 複合型光学素子の製造方法
JP2004161887A (ja) * 2002-11-13 2004-06-10 Konica Minolta Holdings Inc 光硬化性樹脂組成物およびそれを含有するインクジェットインク
JP2005120142A (ja) * 2003-10-14 2005-05-12 Taiyo Ink Mfg Ltd 硬化性組成物、その硬化物及びそれを用いたプリント配線板
JP2005298598A (ja) * 2004-04-08 2005-10-27 Futaba Corp 有機ｅｌ素子用水分吸収剤及び有機ｅｌ素子
WO2014132464A1 (fr) * 2013-02-27 2014-09-04 株式会社オートネットワーク技術研究所 Matériau durcissable à la lumière combinant une aptitude au durcissement anionique et radicalaire

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB9608936D0 (en) * 1995-08-02 1996-07-03 Coates Brothers Plc Printing
US6964999B1 (en) * 1998-02-27 2005-11-15 Kaneka Corporation Polymer and curable composition
JP2006124636A (ja) * 2004-06-28 2006-05-18 Konica Minolta Medical & Graphic Inc 活性光線硬化型組成物、活性光線硬化型インクジェットインク、該活性光線硬化型インクジェットインクを用いた画像形成方法及びインクジェット記録装置
JP5285849B2 (ja) * 2006-10-04 2013-09-11 富士フイルム株式会社 インク組成物、インクジェット記録用インク及びインクジェット記録方法
JP5540862B2 (ja) 2010-04-21 2014-07-02 東洋インキＳｃホールディングス株式会社 Ｕｖ硬化型平版印刷インキおよびその印刷物
JP5634287B2 (ja) 2011-02-07 2014-12-03 Ｄｉｃグラフィックス株式会社 紫外線発光ダイオード硬化性インキ
JP5994393B2 (ja) 2012-05-31 2016-09-21 株式会社リコー 光重合性インクジェットインク、インクカートリッジ、インクジェット印刷装置
US9321856B2 (en) * 2013-12-19 2016-04-26 Exxonmobil Chemical Patents Inc. Process to produce functionalized polymer

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62101670A (ja) * 1985-10-29 1987-05-12 Touka Shikiso Kagaku Kogyo Kk 紫外線硬化型印刷インキ用ゲルワニス
JPH05119201A (ja) * 1991-10-28 1993-05-18 Olympus Optical Co Ltd 複合型光学素子の製造方法
JP2004161887A (ja) * 2002-11-13 2004-06-10 Konica Minolta Holdings Inc 光硬化性樹脂組成物およびそれを含有するインクジェットインク
JP2005120142A (ja) * 2003-10-14 2005-05-12 Taiyo Ink Mfg Ltd 硬化性組成物、その硬化物及びそれを用いたプリント配線板
JP2005298598A (ja) * 2004-04-08 2005-10-27 Futaba Corp 有機ｅｌ素子用水分吸収剤及び有機ｅｌ素子
WO2014132464A1 (fr) * 2013-02-27 2014-09-04 株式会社オートネットワーク技術研究所 Matériau durcissable à la lumière combinant une aptitude au durcissement anionique et radicalaire

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017066348A (ja) * 2015-10-02 2017-04-06 東洋インキＳｃホールディングス株式会社 活性エネルギー線硬化型印刷インキおよび印刷物
US11193028B2 (en) * 2015-11-16 2021-12-07 Ricoh Company, Ltd Active-energy-ray-curable composition, active-energy-ray-curable ink, composition stored container, two-dimensional or three-dimensional image forming method, two-dimensional or three-dimensional image forming apparatus, and processed product
JP2020533451A (ja) * 2017-09-10 2020-11-19 マンキーヴィッチ ゲブリューダー ウント コンパニー （ゲーエムベーハー ウント コンパニー カーゲー）Ｍａｎｋｉｅｗｉｃｚ Ｇｅｂｒ． ＆ Ｃｏ． ＧｍｂＨ＆ Ｃｏ． ＫＧ 再生利用可能なコーティング及び再使用可能なプラスチックに印刷するためのその使用
US11702549B2 (en) 2017-09-10 2023-07-18 Mankiewicz Gebr. & Co. (Gmbh & Co. Kg) Recyclable coatings and use thereof for printing reusable plastics
US11993726B2 (en) 2017-09-10 2024-05-28 Mankiewicz Gebr. & Co. (Gmbh & Co.Kg) Recyclable coatings and use thereof for printing reusable plastics
JP2019073631A (ja) * 2017-10-17 2019-05-16 三菱エンジニアリングプラスチックス株式会社 樹脂組成物および成形品
JP7101465B2 (ja) 2017-10-17 2022-07-15 三菱エンジニアリングプラスチックス株式会社 樹脂組成物および成形品
JP2021509924A (ja) * 2018-01-09 2021-04-08 サン・ケミカル・コーポレーション 第ｉｖ族金属キレート、ならびに放射線硬化性インクおよびコーティング組成物におけるその使用
JP7389035B2 (ja) 2018-01-09 2023-11-29 サン・ケミカル・コーポレーション 第ｉｖ族金属キレート、ならびに放射線硬化性インクおよびコーティング組成物におけるその使用
JP2019178287A (ja) * 2018-03-30 2019-10-17 太陽インキ製造株式会社 インクジェット印刷用の硬化性組成物、その硬化物及びその硬化物を有する電子部品
CN111886300A (zh) * 2018-03-30 2020-11-03 太阳油墨制造株式会社 喷墨印刷用的固化性组合物、其固化物和具有该固化物的电子部件
JP7112170B2 (ja) 2018-03-30 2022-08-03 太陽インキ製造株式会社 インクジェット印刷用の硬化性組成物、その硬化物及びその硬化物を有する電子部品

Also Published As

Publication number Publication date
US20180171037A1 (en) 2018-06-21
JP6536570B2 (ja) 2019-07-03
JPWO2015151833A1 (ja) 2017-04-13
US10011665B1 (en) 2018-07-03

Similar Documents

Publication Publication Date Title
WO2015151833A1 (fr) Composition photodurcissable et encre photodurcissable pour jet d'encre la contenant, procédé d'enregistrement utilisant la composition photodurcissable, et procédé d'enregistrement utilisant l'encre photodurcissable pour jet d'encre
JP5682750B2 (ja) インクジェット記録装置およびインクジェット記録方法
JP5885117B2 (ja) 記録方法
JP6142506B2 (ja) インクジェットインク組成物、インク収容体、インクジェット記録方法
JP4051928B2 (ja) 画像形成方法及び画像形成装置
JP6191120B2 (ja) インクジェット記録方法、インクジェット記録装置
JP2009083267A (ja) インクジェット記録方法
JP5946137B2 (ja) インクジェット記録方法
EP1870440A1 (fr) Encre de jet d' encre durcissable par un rayonnement actinique, et procede pour la formation d image et dispositif d' enregistrement de jet d' encre utilisant ladite encre
JP6832961B2 (ja) ラミネート印刷物の製造方法、及び、ラミネート印刷物
JP7088213B2 (ja) 活性光線硬化型インクジェットインクセット及びインクジェット記録方法
JP7081665B2 (ja) 画像記録方法
JP2011207103A (ja) インクジェット記録装置および画像形成方法
JP6479326B2 (ja) 光硬化性インクジェットインク及び画像形成方法
JP7243166B2 (ja) 画像形成方法
JP2016047652A (ja) インクジェット記録装置および画像形成方法
JP5954552B2 (ja) インクジェット記録装置およびインクジェット記録方法
JP2022149204A (ja) インクジェット記録方法およびインクジェット記録装置
JP6369584B2 (ja) インクジェット記録方法
JP6183481B2 (ja) 記録方法
US12036806B2 (en) Ink jet recording method and ink jet recording apparatus
JP7172506B2 (ja) 放射線硬化型インクジェットインクセット及びインクジェット記録方法
US20220203741A1 (en) Ink Jet Recording Method And Ink Jet Recording Apparatus
JP2003220699A (ja) 画像形成方法及び印刷用原版
WO2016088703A1 (fr) Apprêt, ensemble d'encre et procédé de formation d'image

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 15772272

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2016511530

Country of ref document: JP

Kind code of ref document: A

WWE Wipo information: entry into national phase

Ref document number: 15127636

Country of ref document: US

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 15772272

Country of ref document: EP

Kind code of ref document: A1